Azo dyestuffs



Patented June 11; 1940; a

UNITED STATE ,PATE

NT CE AZO DYESTUFFS Richard Fleischhauer and Heinrich Bitter, Frankforton the Main Fechenheim, Ger- ,ma'ny, assignors to General Aniline & Fihnl Corporation, aacoi'poration of Delaware -No-Dra.wing. Application May12, 1938, Serial son Son-X wherein X stands for member selected from thegroup consisting of ,alkyl, cycloalkyl and aryl groups, aryl meaningvaradicle; of the benzene series and B standing for a member selected fromthe group consisting of radicles of the naphthalene, pyrazolone,hydroxycarbazole and hydroxydiphenylene oxide series. i The newdyestufisare prepared by combining the diazo compoundsof aromatic amines of the pgeneral formula: -1 I l wherein X1 stands for a member selected from thegroup consisting offalkyl, cycloalkyl and aryl groups, aryl meaning aradicle of the'bensene series, with coupling components selectedfronithe group consisting; 1 of ,compounds of the orange to ties.

centigrade.

naphthalene, pyrazolone, hydroxycarbazole and hydroxydiphenylenebxideseries. ff j The new dyestuffstliusobtained dye wool and silk variousshades, especiallyvery clear red to yellow shades or gooq 'fastness'proper- In' order to further illustrate ourinvention the followingexamples; are given, the parts being by weight and all temperatures indegrees Example 1 26.5 parts of l aminobenzene -ethylsulfone-,G-sulfonic acid are dissolved in water with the addition of, sodiumcarbonate. ,Then the necessary, amount; of sodium nitrite is ,addedqandthe mixture is allowed to run into a mixture of ice "andhydrochlorioacid. The suspension of the diazo compound formed is added,whilecooling, to,,a,solution. of 29 partspof 12 acetylamino-5-hydroxymaphthaleneflfsulfonic acid, containing No. 207,506. In GermanyMay 18,1337

3 Claims. (01. 260-198) This invention relates toi azodyestufis, moreparticularly to those of; the general, formula; 3

an excess of sodium bicarbonate.

is separated and dried. w-It islan orange-red powder, solubleinwater anddyeing wool and silkvery yellowish orangeshades of very good.

.fastness to light and seawater and good fastness to'iwashing andperspiration. The dyestufi :has

a good levelling power and'is iast to alkalies.

, As a by-jproduct there is formedalittle amount water and the shade ofwhich is turned to darkred in the presence ofalkalies.

By employing l-hydroxynaphthalene 3-sulfonic acid as coupling componenta dyestuff is obtained which yields similar Shadesof likewise very goodfastness to light, whereas the dyestuff obtained by using 2-(pchlormpropionylamino) -5-hydroxynaphthalene-T-sulfonic"acid isdistinguished by a somewhat better fastness to washing and;perspiration.

Dyestuffs which yield more yellowish-shades are obtained by employing ascoupling components 2-hydroxynaphthalene-sulfonic acids, for instance2-hydroxynaphthalene-6.7- or 8- sulfonic acid or2-hydroxynaphthalene-6.8-disulfonic acid, whereas more reddish orangeshades are obtained by meansno f dyestufis which contain as couplingcomponents the radicles of 2- j benzoylamino 5hydroxynaphthalene-7-sulfonic of an orange dyestuff which is moresoluble in,

acid or, 1 benzoylamino-5-hydroxynaphthalene- '7-sulfonicacid. W v,

The l-aminobenzene-3-ethylsulfone 6 sulfonic acid employed as diazocomponent for the above example which has hitherto not been described,

,may be prepared for example in the following manner; l-chlorothiophenolis ethylated and then converted by oxidation into the correspond ings'ulforie compound. The 4-c hloropl enyl-ethyls'ulfone obtainedisnitrated and then treated l sodium sulfite whereby the 1-nitrobenZene3- ethylsulfone-fS-sulfonicacid is obtained which is reduced to thecorresponding amine. The 1 amino-3 ethylsulfone 6-su1fonic acidis easilysoluble in solutions ,of sodium carbonate or acetate andjslightlysolublein water or, hydrochloric acid. The corresponding diazo com-{pounds-are slightly soluble in water. a

Example 2 29.3 parts of 1aminobenzene3-n-buty1sulfone- 6-sulfonic acidare diazotized and the suspension of the diazo compound formed isallowed to run into a solution of 29 parts of l-acetylamino- 5-hydroxynaphthalene-'7-sulfonic acid containing an excessofljsodiuma'cetate. 'Then the'mixture is stirred for some hours. Whenthe combination is complete, the dyestufi formed of the formula; :'Iiu

SOsNa is precipitated by the addition of sodium chloride, filtered offand dried. It {is a reddish brown powder, soluble in water and dyeingwool orange shades of good fastriess to light,seawater and perspiration.The dyestufi has a good levelling power.

The l-aminobenzene-B-n-butylsu1fone-,6 -sulionic acid employed as diazocomponent may be prepared in an analogous manner as described in Example1 for the manufacture of- 'the dia zo I component of Example 1. i l

By employing 2acetylamino-B-hydroxynaphthalene-G-sulfonic acid or1-acetylamino-8-hy droxynaphthalene 6-sulfonic acid 1 as couplingcomponent similar dyestuffs are obtained which yield somewhat morereddish orange shades.

. Eacancples 25.1 parts of l-aminobenzenee3 methylsulfonefi-sulfonicacid are diazotizedand the suspension of the diazo compound formed iscombined with a solution of 24 parts of, 2.-amino-8hydroxynaphthalene-6-sulfonio acid;- containing;

a little amount of'mineral acid, The' mixture is stirred for some hours,then the dyestuffformed of the formula: v

' some NH; N=N

80 011 some I is separated and dried. It is a violettish-brown powder,soluble in water and dyeing-wool clear red shades of excellent fastnessto light. The dyestufi has a good levelling power.

The analogous dyestufis prepared by employing 1- aminobenzene 3-ethylsulfone -6- sulfonic acid or'1aminobenzene-SbenzylSulfone-fi-sulfonic' acid as diazo components dyewool similar shades which are distinguished by asomewhat better fastnessto washing and perspiration.

' Examples 29.3 parts of 1aminobehzene-B-n butylsulfone-G-sulfonic acidare diazotized and the diazo compound obtained is combined with asolution of 26 parts of 2-methylaminonaphthalene-7 sulfonic acidcontaining a-little amount of mineral isfwhen dry, a red powder, solublein water and dyeing wool bright scarlet shades.

- fi-sulfonic acid are diazotized and the diazo comacid. The sodium ofthe formula:

salt of the dyestuff formed NH-CHI S Or-C H;

CH: ta

, Example 5 31.3 parts of 1aminobenzene-3-phenylsulfonepound formed iscombined with a solution of 25 parts of 1- (2' ,5 diachlorophenyl')'3'-methyl-5 pyrazolone containing an" excess'of sodium car-' bonate.The dyestuff formedof the formula:

SOaNa By replacing the above diazo component by, the" 50 correspondingamount of 1- aminobenezene-3 cyclohexylsulfone-Gsulfonic acid,dyestuffs; of similar properties are obtained.,

26.5 parts of .1-aminobenzene 3-ethylsulfone '55 G-sulfonic acid arediazotifzed and the 'diaz'o com-' pound formed is combined with asolutionfof I44 parts of 2-hydroxynaphthalenecontaining an e cess' ofsodium hydroxide. 'The dyestufi formed. of the formulaz; I s

SIOzNa SOr-ChHts v is precipitated by "the addition of 3 sodiumbicarbonate, filtered oif and'dried; I It is an mangebrown powder,soluble in water and dyeing wool from an acid bath orangeshades 'of goodfast ness-properties.- f r l By employing'2-hydroxycarbaaoleflor3-li'ydiox ydiphenyleneoxide as" coupl ng components; dye

wherein X stands for a member selected from 20 the group consisting ofalkyl, cycloalkyl andaryl 9 groups of the benzene series, and B standsfor y the radicle of a coupling component selected from the groupconsisting of compounds of the naphthalene, pyrazolone, hydroxycarbazoleand hy- 25 droxydiphenylene oxide series, which dyestuffs dye wool andsilk various shades of good fastness properties.

2. The azo dyestufi of the formula:

som o NaOsS- NH-C o-c H:

S0r-C2 t which dyestuif is an orange-red powder, soluble in water anddyeing wool and silk very yellowish- SOaNB NH:

1 l i i Soar-4111a SOaNa which dyestufi is a violettish-brown powder,

soluble in water and dyeing wool and silk clear red shades of excellentfastness to light.

RICHARD FIEISCHHAUER. HEINRICH RITTER.

